KR100301382B1 - A water-soluble coating composition based on a binder which can be dissolved or diluted in water made of silicone elastomer copolymer particles crosslinked in advance with an organopolymer shell, and a method of manufacturing the same. - Google Patents
A water-soluble coating composition based on a binder which can be dissolved or diluted in water made of silicone elastomer copolymer particles crosslinked in advance with an organopolymer shell, and a method of manufacturing the same. Download PDFInfo
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
- C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
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- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/68—Particle size between 100-1000 nm
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
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- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/902—Core-shell
Abstract
오르가노폴리머쉘을 가진 사전에 가교시킨 실리콘 엘라스토머 코폴리머 입자는 물에 용해시킬 수 있거나 또는 물에 희석시킬 수 있는 바인더를 기재로 한 수용성 코팅 조성물을 조성하는 성분으로 사용된다.Pre-crosslinked silicone elastomer copolymer particles with organopolymer shells are used as components to form a water-soluble coating composition based on a binder that can be dissolved in water or diluted in water.
그 실리콘 엘라스토머 입자에는 (a)그 코폴리머의 전체 중량을 기준으로하여 일반식(R2SiO2/2)x· (R'SiO3/2)y· (SiO4/2)z(여기서 x=5 ∼ 99.5㏖%, y=0.5 ~ 95wt%, z= 0 ∼ 30㏖% 임)의 코어폴리머 5∼95wt%와,The silicone elastomer particles contain (a) general formula (R 2 SiO 2/2 ) x · (R'SiO 3/2 ) y · (SiO 4/2 ) z (where x based on the total weight of the copolymer) 5 to 95 wt% of a core polymer of 5 to 99.5 mol%, y = 0.5 to 95 wt%, z = 0 to 30 mol%,
b) 그 코폴리머의 전체 중량을 기준으로 하여 모노 또는 폴리에틸렌 불포화 모노머의 오르가노폴리머쉘 5∼95wt%를 포함하며, R은 같거나 다른 1가의 탄소원자 1~6개를 가진 알킬 또는 알케닐래디컬, 아릴래디컬 또는 치환탄화수소래디컬이다.b) 5 to 95 wt% of an organopolymer shell of mono or polyethylene unsaturated monomers, based on the total weight of the copolymer, R is an alkyl or alkenyl radical having from 1 to 6 monovalent carbon atoms, the same or different , Aryl radicals or substituted hydrocarbon radicals.
Description
수용성 코팅재는 물에 용해시킬 수 있거나 희석시킬 수 있는 바인더로 구성되어있다.Water-soluble coatings consist of binders that can be dissolved or diluted in water.
물에 희석시킬 수 있는 바인더에는 수지성분과, 유화시키거나 자기유화시킬 수 있는(self-emulsifiable)수지와 수용성 분산액이 있다Diluents in water include resin components, emulsified or self-emulsifiable resins, and aqueous dispersions.
물에 용해시킬 수 있는 바인더의 예로는 개질알키드수지 , 아크릴레이트수지, 선상 또는 분기상 포화 폴리에스테르수지, 에폭시수지 , 쉘락(shellac) 및 변성페놀수지가 있다.Examples of binders that can be dissolved in water include modified alkyd resins, acrylate resins, linear or branched saturated polyester resins, epoxy resins, shellac and modified phenolic resins.
물에 희석시킬 수 있는 바인더의 예로는-광개질시킨-분산성이 있거나, 또는 물에 분산시킬 수 있는 불포화 또는 포화 폴리에스테르수지, 알키드수지에멀젼, 폴리우레탄분산액, 1성분 에폭시수지에멀젼, 유화시킬 수 있는 2성분 에폭시수지계, 분산성알키드, 페놀, 멜라민 및 우레아수지, (메타)아크릴레이트분산액, (메타)아크릴 레이트 코폴리머분산액, 폴리스티렌 및 스티렌 코폴기머 분산액, 폴리(비닐에테르)분산액, 폴리비닐클로리드 및 폴리비닐리덴 클로리드 분산액이 있다.Examples of binders that can be diluted in water are unsaturated or saturated polyester resins, alkyd resin emulsions, polyurethane dispersions, one-component epoxy resin emulsions, emulsifiable or photodispersed-dispersible, or dispersible in water. 2-component epoxy resins, dispersible alkyds, phenols, melamines and urea resins, (meth) acrylate dispersions, (meth) acrylate copolymer dispersions, polystyrene and styrene copolmer dispersions, poly (vinyl ether) dispersions, polyvinyl Chloride and polyvinylidene chloride dispersions.
물에 용해시킬 수 있거나 물에 희석시킬 수 있는 바인더 외에, 수용성 코팅재에는 일반적으로, 안료, 필러, 수용성 가교제 및 가교촉매, 예로서 레벨링조제(levelling assistants), 액화조제 및 습윤제(wetting agents)등의 첨가제가 포함된다.In addition to binders that can be dissolved in water or diluted in water, water-soluble coatings generally include pigments, fillers, water-soluble crosslinkers and crosslinking catalysts such as leveling assistants, liquefaction aids and wetting agents. Additives are included.
이들의 조성물은 수용성 형태로 예로서 금속기재, 광물기재 플라스틱, 목재, 종이 또는 글라스 등에 처리한다.These compositions are treated in water-soluble form, for example metal-based, mineral-based plastics, wood, paper or glass.
처리후, 그 수용성 필름은 고상의 코팅필름으로 될 때가지 건조한다.After treatment, the water-soluble film is dried until it becomes a solid coating film.
대기온도(실온)에서 건조한 필름은 대기중에서 건조한 후 100℃ 이내의 온도에서 선택적으로 열조절/후건조 시킨다.Films dried at ambient temperature (room temperature) are optionally heat-controlled and post-dried at temperatures within 100 ° C after drying in the atmosphere.
다른 종류의 수용성 코팅재에 있어서 2종이상의 바인더성분의 화학반응(후가교)을 필요로 할 경우 필름형성에 더 높은 온도(120-220℃)가 필요하다.In other types of water-soluble coatings, higher temperatures (120-220 ° C.) are required for film formation when chemical reactions (post-crosslinking) of two or more binder components are required.
위에서 예시한 물에 용해시킬 수 있거나 희석시킬 수 있는 바인더는 주로 열가소성 또는 열경화성 폴리머로 구성되어있어 이들의 폴리머는 일반적으로 경질이나 위약(brittle)하다.Binders that can be dissolved or diluted in water as exemplified above consist primarily of thermoplastic or thermoset polymers so that their polymers are generally hard or brittle.
따라서, 그 필름 특성을 개량시키기 위하여 이들 폴리머에의 충격개질이 필요하다.Therefore, impact modification to these polymers is necessary to improve the film properties.
실리콘 열가소성 및 열경화성 개질제로 공지되어 있으며, 그 충격강도를 증가시킬 뿐만 아니라 저온가요성(fiexibility), 내후성의 안정성(weathering stability), 온도변화에 대한 안정성 및 열가소성 또는 열경화성 오르가노폴리머계의 내약품성을 향상시키므로 특히 관심있는 물질이다.Known as silicone thermoplastic and thermoset modifiers, they not only increase their impact strength, but also have low temperature flexibility, weathering stability, resistance to temperature changes and chemical resistance of thermoplastic or thermosetting organopolymer systems. It is of particular interest as it improves.
그러나, 일반적인 결점은 기본적으로 실리콘과 오르가노폴리머의 불상용성(incompatibility)에 있다.However, a common drawback is basically the incompatibility of silicon and organopolymers.
그 불상용성은 사용과정에서 유동결함(flow defects)을 유발할 수 있고, 동시에 그 실리콘의 이행(migration)으로 접착문제와, 오버코팅적합성(overcoatability)에 따르는 문제가 발생한다.The incompatibility can cause flow defects in use, and at the same time the migration of the silicon leads to adhesion problems and overcoatability.
특허문헌 DE-A 3922285(=GB-A 2222167)(Dow Corning, 1990.1.25.공개)에서는 공지의 오르가노폴리머를 가진 실록산의 불상용성에 대하여 장식용으로 연구개발한 바 있다.Patent document DE-A 3922285 (= GB-A 2222167) (Dow Corning, published on January 25, 1990) has been researching and developing the incompatibility of siloxanes with known organopolymers.
이 특허문헌에서는 햄머 표면효과(hammered surface effect)를 얻기 위하여 폴리디오르가노실록산과, 필름형성폴리머재 수용성 분산액으로 이루어진 코팅 조성물에 대하여 기재되어있다.This patent document describes a coating composition composed of polydiorganosiloxane and a film-forming polymer material aqueous dispersion in order to obtain a hammered surface effect.
이와같은 종류의 폴리실록산은 이산입자(discrete particles)보다 수상중에서의 액체로서 유화형태로 존재하기 때문에 수용성 코팅재의 충격개질에 적합하지 않다.Polysiloxanes of this kind are not suitable for impact modification of water-soluble coatings because they exist in emulsified form as liquid in the water phase rather than discrete particles.
충격개질의 사용에 필요한 양으로 이들의 화합물이 코팅필름에서 배출되었다.These compounds were released from the coating film in the amount required for the use of impact modification.
특허문헌 EP-A 586048(Shin Etsu, 1994 3.9공고)에서는 표면장력을 감소시켜 기재의 습윤성을 향상시키기 위하여 수용성 코팅재에 첨가제로서 디올-작용 실리콘오일에 대하여 기재되어있다.Patent document EP-A 586048 (published by Shin Etsu, 1994 3.9) describes a diol-functional silicone oil as an additive in a water-soluble coating material in order to reduce the surface tension and improve the wettability of the substrate.
여기서, 이들의 실록산은 폴리에테르-개질 실리콘오일보다 더 우수한 유동특성을 나타낸다.Here, their siloxanes exhibit better flow properties than polyether-modified silicone oils.
유화형태로 존재한 이와같은 종류의 실록산은 충격개질에 적합하지 않다.Siloxanes of this kind present in emulsion form are not suitable for impact modification.
이 특허문헌에서는 사용량 ＞ 5wt%에서 이들 화합물로 개질시킨 폴리머필름의 기계적강도가 감소되었다.In this patent document, the mechanical strength of the polymer film modified with these compounds was reduced at the amount of> 5 wt%.
특허문헌 WO-A 93/14169(Crompton Garland Ltd, 1993.7.22.공고)에서는 가교시킬 수 있는 수용성 페놀수지에멀젼과 실리콘수지에멀젼으로 이루어진 조성물에 대하여 기재되어있다.Patent document WO-A 93/14169 (Crompton Garland Ltd, published on July 2, 1993) describes a composition consisting of a water-soluble phenolic resin emulsion and a silicone resin emulsion that can be crosslinked.
페놀수지성분의 가교과정에서 페놀수지에 실리콘이 화학적으로 결합되어 있어, 그 결과 실리콘성분이 가소제로서 페놀수지 매트릭스에 포함된다.In the crosslinking process of the phenol resin component, the silicon is chemically bonded to the phenol resin, and as a result, the silicone component is included in the phenol resin matrix as a plasticizer.
특허문헌 US-A 4803233(Dow Corning, 1989,2,7.특허취득)에서는 오르가노폴리머, 실리콘수지 및 3종의 서로 다른 비이온 유화제의 조합물로 이루어진 수용성 혼합물에 대하여 기재되어있다.Patent document US-A 4803233 (Dow Corning, 1989,2,7., Patented) describes an aqueous mixture consisting of an organopolymer, a silicone resin and a combination of three different nonionic emulsifiers.
폴리머계와 실리콘성분에 따라 실리콘수지를 첨가시켜(어떤 경우에는 균질블렌드를 열처리한 후에만 첨가)그 코팅재의 인장강도, 접착성 및 내식성을 향상시킨다.Depending on the polymer type and the silicone component, silicone resins are added (in some cases only after heat treatment of the homogeneous blend) to improve the tensile strength, adhesion and corrosion resistance of the coating.
경도를 유지시킨 충격강도의 향상에 대해서는 특허문헌 WO-A 93/14169 또는 US-A 4803233에서 기재된 바 없다.The improvement of the impact strength which kept hardness was not described in patent document WO-A 93/14169 or US-A 4803233.
이들의 물질은 오르가노폴리머와 상용성인 입자구조를 가진 개질제를 포함하지 않고 있으므로 미상분리(mirophase separation)를 조절할 수 없다.Since these materials do not contain a modifier having a particle structure compatible with the organopolymer, microphase separation cannot be controlled.
특허문헌 EP-A 541395(Takemoto, 1993.5.12.공고)에서는 폴리실록산-폴리비닐 그라프트 코폴리머의 수용성 에멀젼을 기재로 하는 열가소성 폴리에스테르필름의 수용성 코팅 조성물에 대하여 기재되어 있다.Patent document EP-A 541395 (Takemoto, published May 1, 1993) describes a water-soluble coating composition of a thermoplastic polyester film based on a water-soluble emulsion of a polysiloxane-polyvinyl graft copolymer.
이들의 수용성 바인더계는 평활성(smoothness), 이형성, 발수성 및 발유성(oil-repellency)등 폴리에스테르 필름의 표면 특성을 향상시킨다.These water-soluble binder systems improve the surface properties of polyester films such as smoothness, release property, water repellency and oil-repellency.
이 경우, 그라프트 코폴리머는 수용성 코팅재중에서 오르가노폴리머 바인더의 개질제로서 사용되지 않으나, 열가소성 폴리머필름에 처리할 때 소정의 표면특성을 얻을 수 있는 수용성 코팅 조성물로서 사용된다.In this case, the graft copolymer is not used as a modifier of the organopolymer binder in the water-soluble coating material, but is used as a water-soluble coating composition which can obtain a predetermined surface property when processed to a thermoplastic polymer film.
특허문헌 WO-A 90/08810(ICI Australia Operations Proprietary Ltd., 1990.8.0공고)에서는 실리콘 함유 폴리머, 즉 "멀티-폴리머"(multi-polymer)입자를 기재로 한 수용성 코팅 조성물에 대하여 기재되어있다.Patent document WO-A 90/08810 (ICI Australia Operations Proprietary Ltd., published Aug. 1990) describes a water-soluble coating composition based on silicone-containing polymers, ie, "multi-polymer" particles. .
그 "멀티-폴리머입자"는 실리콘폴리머를 가진 혼합물 중에서 모노머를 중합시켜 제조한다.The "multi-polymer particles" are prepared by polymerizing monomers in a mixture with a silicone polymer.
이 경우, 실리콘성분은 폴리머를 제조하기 전에 그 모노머/모노머에 첨가시켜야 하며, 조성성분으로서 수용성 바인더계에 첨가할 수 없다.In this case, the silicone component must be added to the monomer / monomer before preparing the polymer, and cannot be added to the water-soluble binder system as a component.
이 경우 얻어진 물에 용해시킬 수 있는 바인더계에서 실리콘 성분은 예로서 코팅재의 UV 안정성을 향상시킨다.In this case, the silicone component in the binder system which can be dissolved in the obtained water improves UV stability of the coating material, for example.
그 충격강도의 개량에 대해서는 기재된 바 없다.The improvement of the impact strength is not described.
또, 사용한 성분은 오르가노폴리머와 상용성이 있는 입상구조를 가진 개질제로 이루어지지 않은 액체 또는 수지이므로, 이 경우 조정된 미상분리(controlled microphase separation)가 없다.In addition, since the component used is a liquid or resin which is not composed of a modifier having a granular structure compatible with the organopolymer, there is no controlled microphase separation in this case.
또, 특허문헌 EP-A 492376(US-A5223586, Wacker-Chemie Gmbh;1993.06.29. 특허취득)에서는 코어/쉘구조를 가진 엘라스토머 그라프트 코폴리머(elastomeric graft copolymers)와 그 제조방법에 대하여 기재되어있다.In addition, Patent Document EP-A 492376 (US-A5223586, Wacker-Chemie Gmbh; obtained patent on 1993.06.29.) Discloses elastomeric graft copolymers having a core / shell structure and a method of manufacturing the same. have.
이 코폴리머는 특히 열가소성 몰딩 조성물의 첨가제로서 사용하는 데 한정되어 있다.This copolymer is in particular limited to use as an additive in thermoplastic molding compositions.
수용성 코팅 조성물의 개질에서 이와같은 입자상 코폴리머의 사용에 대하여 어떤 암시나 구체적 내용이 기재된 바 없다.No indications or details have been made regarding the use of such particulate copolymers in the modification of water soluble coating compositions.
이 발명은 오르가노폴리머쉘을 가진 사전에 가교시킨 실리콘 엘라스토머 코 폴리머 입자로 이루어진 물에 용해시킬 수 있거나 물에 희석시킬 수 있는 바인더를 기재로 한 수용성 코팅 조성물에 관한 것이다.This invention relates to a water-soluble coating composition based on a binder that can be dissolved in or diluted with water consisting of precrosslinked silicone elastomeric copolymer particles with an organopolymer shell.
또, 이 발명은 바인더와 오르가노폴리머쉘을 가진 사전에 가교시킨 실리콘 엘라스토머 코폴리머를 물에 첨가시켜 물에 용해시킬 수 있거나 또는 물에 희석시킬 수 있는 바인더를 기재로 한 수용성 코팅 조성물의 제조방법에 관한 것이다.The present invention also provides a method for preparing a water-soluble coating composition based on a binder which can be dissolved in water or diluted with water by adding a pre-crosslinked silicone elastomer copolymer having a binder and an organopolymer shell to water. It is about.
이 발명은 물에 용해시킬 수 있거나 물에 희석시킬 수 있는 바인더를 기재로 한 수용성 코팅 조성물의 하나의 조성성분으로 오르가노폴리머쉘(organopolymer shell)을 가진 사전에 가교시킨 실리콘 엘라스토머 코폴리머 입자의 사용에 관한 것이다.This invention uses the use of pre-crosslinked silicone elastomer copolymer particles having an organopolymer shell as one component of a water-soluble coating composition based on a binder that can be dissolved in water or diluted in water. It is about.
이 발명은 오르가노폴리머 바인더를 기재로 한 수용성 코팅 조성물의 개질제, 즉 오르가노폴리머 바인더와 상용성이 높고, 경도, 치수안정성 및 기계적 강도 등 기존의 바람직한 폴리머특성을 유지함과 동시에 취득할 수 있는 필름의 충격강도를 향상시킬 수 있는 수용성 코팅재를 제공하는 데 그 목적이 있다.The present invention has a high compatibility with the modifier of the water-soluble coating composition based on the organopolymer binder, that is, the organopolymer binder, and can be obtained while maintaining existing desirable polymer properties such as hardness, dimensional stability, and mechanical strength. The purpose is to provide a water-soluble coating that can improve the impact strength of.
이 발명은 바인더와 오르가노폴리머쉘(shell)을 가진 사전에 가교시킨 실리콘 엘라스토머 코폴리머 입자를 물에 첨가시켜 물에 용해시킬 수 있거나 물에 희석시킬 수 있는 바인더를 기재로한 수용성 코팅 조성물을 제조하는 방법에 있어서, 그 실리콘 엘라스토머 코폴리머 입자는The present invention provides a water-soluble coating composition based on a binder that can be dissolved in water or diluted in water by adding pre-crosslinked silicone elastomer copolymer particles with a binder and an organopolymer shell. In the method, the silicone elastomer copolymer particles
a) 그 코폴리머의 전체 중량을 기준으로하여 일반식(R2SiO2/2)x· (RSiO3/2)y, · (SiO4/2)2(여기서 x= 5 ~ 99.5㏖%, y=0.5 ∼ 95mo1%, z= 0 ∼ 30㏖%)의 코어폴리머(core polymer) 5 ∼ 95wt%와,a) general formula (R 2 SiO 2/2 ) x (RSiO 3/2 ) y , (SiO 4/2 ) 2 (where x = 5 to 99.5 mol%, based on the total weight of the copolymer, y = 0.5 to 95 mo1%, z = 0 to 30 mol%) of 5 to 95 wt% of the core polymer,
b) 그 코폴리머의 전체 중량을 기준으로 하여 모노 또는 폴리에틸렌 불포화 모노머의 오르가노폴리머쉘(shell) 5-95wt%로 이루어지며, 위 일반식에서 R은 탄소원자 5~6개를 가진 같거나 다른 1가의 알킬 또는 알케닐래디컬, 아릴래디컬 또는 치환탄화수소래디컬임을 특징으로 한다.b) 5-95 wt% of an organopolymer shell of mono or polyethylene unsaturated monomers, based on the total weight of the copolymer, in which R is the same or different with 1 to 5 carbon atoms It is characterized in that the alkyl or alkenyl radical, aryl radical or substituted hydrocarbon radical.
이 발명은 오르가노폴리머쉘을 가진 사전에 가교시킨 실리콘 엘라스토머코폴리머 입자로 이루어진 물에 용해시킬 수 있거나 물에 희석시킬 수 있는 바인더를 기재로 한 수용성 코팅 조성물에 있어서,The present invention relates to a water-soluble coating composition based on a binder that can be dissolved in water or diluted in water consisting of pre-crosslinked silicone elastomer copolymer particles having an organopolymer shell,
그 실리콘 엘라스토머 코폴리머 입자는The silicone elastomer copolymer particles
a) 그 코폴리머의 전체 중량을 기준으로 하여 일반식(R2SiO2/2)x· (RSiO3/2)y, · (SiO4/2)2(여기서 x= 5 ~ 99.5㏖%, y=0.5 ∼ 95mo1%, z= 0 ∼ 30㏖%)의 코어폴리머 5 ∼ 95wt%와,a) general formula (R 2 SiO 2/2 ) x (RSiO 3/2 ) y , (SiO 4/2 ) 2 , where x = 5 to 99.5 mol%, based on the total weight of the copolymer, y = 0.5 to 95 mo1%, z = 0 to 30 mol%) of 5 to 95 wt% of the core polymer,
b) 그 코폴리머의 전체 중량을 기준으로 하여 모노 또는 폴리에틸렌 불포화 모노머의 오르가노폴리머쉘 5-95wt%로 이루어지며, R은 탄소원자 1~6개를 가진 같거나 다른 1가의 알킬 또는 알케닐래디컬, 아릴래디컬 또는 치환탄화수소래디컬임을 특징으로 하는 수용성 코팅 조성물을 제공한다.b) 5-95 wt% of an organopolymer shell of mono or polyethylene unsaturated monomers, based on the total weight of the copolymer, R is the same or different monovalent alkyl or alkenyl radical having 1 to 6 carbon atoms It provides a water-soluble coating composition, characterized in that the aryl radical or substituted hydrocarbon radical.
오르가노폴리머쉘을 가진 사전에 가교시킨 실리콘 엘라스토머 코폴리머 입자는Pre-crosslinked silicone elastomer copolymer particles with organopolymer shell
a) 그 코폴리머의 전체 중량을 기준으로 하여 일반식(R2SiO2/2)x· (RSiO3/2)y, · (SiO4/2)2(여기서 x= 5 ~ 99㏖%, y=1 ∼ 50mo1%, z= 0 ∼ 20㏖%)의 코어폴리머 20∼30wt%와,a) general formula (R 2 SiO 2/2 ) x (RSiO 3/2 ) y , (SiO 4/2 ) 2 , where x = 5 to 99 mol%, based on the total weight of the copolymer, y = 1 to 50 mo1%, z = 0 to 20 mol%) of 20 to 30 wt% of the core polymer,
b) 그 코폴리머의 전체 중량을 기준으로 하여 모노 또는 폴리에틸렌 불포화 포노머의 오르가노폴리머쉘 20∼80wt%로 이루어지는 것이 바람직하다(여기서 R은 위에서의 정의와 같다).b) preferably 20 to 80 wt% of the organopolymer shell of the mono or polyethylene unsaturated phenomeric based on the total weight of the copolymer (where R is as defined above).
위에서 설명한 수용성 코팅 조성물의 제조방법 및 그 수용성 코팅 조성물에 그 코어폴리머의 양이 너무 적으면 탄성을 도입할 수 없고, 너무 많으면 오르가노폴리머쉘의 적은양 때문에 불충분한 상용성만이 얻어저 그 코어폴리머는 5∼95wt%의 범위가 적합하다.The method for preparing the water-soluble coating composition described above and the amount of the core polymer in the water-soluble coating composition are too small to introduce elasticity, and if the amount is too high, only insufficient compatibility is obtained due to the small amount of the organopolymer shell. The range of 5-95 wt% is suitable.
그 래디컬 R은 메틸, 에틸, n-프로필, 이소프로필, n-부틸, sec-부틸, 아밀 헥실래디컬 등 알킬래디컬; 비닐, 알릴, 부테닐 및 1-헥세닐래디컬 등 알케닐래디컬; 페닐래디컬 등 아릴래디컬, 또는 할로겐화탄화수소래디컬, 메르캅토알킬래디컬, 시아노알킬래디컬, 아미노알킬래디컬, 아실옥시알킬래디컬, 히드록시알킬래디컬 등 치환탄화수소래디컬이 바람직하다.Radical R is alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, amyl hexyl radical; Alkenyl radicals such as vinyl, allyl, butenyl, and 1-hexenyl radicals; Aryl radicals such as phenyl radicals or substituted hydrocarbon radicals such as halogenated hydrocarbon radicals, mercaptoalkyl radicals, cyanoalkyl radicals, aminoalkyl radicals, acyloxyalkyl radicals and hydroxyalkyl radicals are preferable.
특히 바람직한 래디컬에는 메틸, 에틸, 프로필, 페닐, 비닐, 알릴, 1-헥세닐, 3-메타아크릴옥시프로필 및 3-메르캅토프로필이 있으며, 예로서 실록산 폴리머에서 30㏖% 이하의 래디컬에는 비닐기, 3- 메타아크릴옥시프로필 또는 3-메르캅토프로필기가 있다.Particularly preferred radicals include methyl, ethyl, propyl, phenyl, vinyl, allyl, 1-hexenyl, 3-methacryloxypropyl and 3-mercaptopropyl, eg radicals up to 30 mol% in siloxane polymers are vinyl groups. , 3-methacryloxypropyl or 3-mercaptopropyl group.
오르가노폴리머성분(b)의 모노머로서 아크릴에스테르 또는 메타아크릴에스테르, 푸마르산 및 말레인산과 탄소원자 1-10개를 가진 디올 및 지방족알코올의 모노 및 디에스테르, 아크릴아마이드와 메타아크릴아마이드, 아크릴로니트릴, 스티렌, P-메틸스티렌, O-메틸스티렌, 디비닐벤젠, 비닐아세테이트, 비닐프로피오네이트, 말레이미드(maleimides), 비닐클로리드, 모노 및 디비닐에테르, 에틸렌, 부타디엔, 이소프렌 및 클로로프렌을 사용하는 것이 바람직하다.Monomers and diesters of acrylic esters or methacrylic esters, fumaric acid and maleic acid with diols and aliphatic alcohols having 1 to 10 carbon atoms, acrylamide and methacrylamide, acrylonitrile, Using styrene, P-methylstyrene, O-methylstyrene, divinylbenzene, vinyl acetate, vinylpropionate, maleimides, vinyl chloride, mono and divinyl ether, ethylene, butadiene, isoprene and chloroprene It is preferable.
스티렌 및 아크릴에스테르와 탄소원자 1-4개를 가진 지방족 알코올의 메타아크릴에스테르, 예로서 메틸(메타)아크릴레이트, 부틸(메타)아크릴레이트 및 글리시딜(메타)아크릴레이트가 특히 바람직하다.Particular preference is given to styrene and acrylic esters and methacrylic esters of aliphatic alcohols having 1-4 carbon atoms, such as methyl (meth) acrylate, butyl (meth) acrylate and glycidyl (meth) acrylate.
호모폴리머와 이들 모노머의 코폴리머가 오르가노폴리머 성분으로 적합하다.Homopolymers and copolymers of these monomers are suitable as organopolymer components.
그 사전에 가교시킨 실리콘 엘라스토머 코폴리머 입자는 평균입자직경 10-300㎚, 특히 30-150㎚을 갖는 것이 바람직하다.The previously crosslinked silicone elastomer copolymer particles preferably have an average particle diameter of 10-300 nm, in particular 30-150 nm.
즉, 위에서 설명한 수용성 코팅 조성물에서 그 코폴리머입자가 거칠 경우 입자표면의 품질이 감소되고, 그 입자가 너무 작을 경우 탄성효과가 감소되어 그 평균입자직경은 10-300㎚의 범위를 가진다.That is, in the above-mentioned water-soluble coating composition, when the copolymer particles are coarse, the particle surface quality is reduced, and when the particles are too small, the elastic effect is reduced, and the average particle diameter is in the range of 10-300 nm.
그 입자직경은 위 범위내에서 변동되며, 다분산성 인덱스(poly dispersity index) δ2=0.2이하를 가진 1개 모드의 입자크기 분포로 존재하는 것이 바람직하다.The particle diameter varies within the above range and is preferably present in one mode of particle size distribution with a poly dispersity index δ 2 = 0.2 or less.
그 폴리실록산 그라프트 기재는 에멀젼 중합에 의해 그 타입 RaSi(OR')4-a(a=0, 1 또는 2임)의 모노머실란 또는 바람직하게는 일반식(R2SiO)n(여기서 n=3-8임)의 저분자량의 실록산의 대응되는 혼합물중에서 교반시킨 유화제/물 혼합액에 혼합시켜 제조한다.The polysiloxane graft substrate is produced by emulsion polymerization of monomer silanes of the type R a Si (OR ′) 4-a (a = 0, 1 or 2) or preferably of the general formula (R 2 SiO) n where n 3-8) in a corresponding mixture of low molecular weight siloxanes.
그 래디컬 R은 위에서 설명한 정의를 가진다.The radical R has the definition described above.
R'는 탄소원자 1-6개를 가진 알킬래디컬, 아릴래디컬 또는 치환탄화수소래디컬을 나타내며 메틸 및 프로필래디컬이 바람직하다.R 'represents alkyl radicals, aryl radicals or substituted hydrocarbon radicals having 1-6 carbon atoms, with methyl and propyl radicals being preferred.
실란 또는 실란혼합물 또는 실란/실록산혼합물은 혼합 형태로 첨가한다.Silanes or silane mixtures or silane / siloxane mixtures are added in mixed form.
그 에멀젼중합은 온도 30-90℃, 바람직하게는 60-85℃에서 대기압하에 실시한다.The emulsion polymerization is carried out under atmospheric pressure at a temperature of 30-90 ° C, preferably 60-85 ° C.
그 중합 혼합액의 pH는 1-4, 바람직하게는 2-3이다.The pH of the polymerization mixture is 1-4, preferably 2-3.
적합한 유화제와 그 사용량은 특허문헌 EP-A 492376에 기재되어있다.Suitable emulsifiers and their amounts of use are described in patent document EP-A 492376.
1개 모드 입자크기분포(monomodall particle size distribution)를 얻기위하여 폴리실록산 그라프트 기재를 제조할 때 균질화 처리공정을 생략하는 것이 바람직하다.In order to obtain a monomodal particle size distribution, it is desirable to omit the homogenization process when preparing the polysiloxane graft substrate.
또 다른 바람직한 실시예에서, 폴리실록산 그라프트 기재의 중합을 완료시킨 다음, 그 중합에서 생성된 알코올과 다른 휘발성분을 증발에 의해 제거한다.In another preferred embodiment, the polymerization of the polysiloxane graft base is completed and then alcohol and other volatiles produced in the polymerization are removed by evaporation.
적합한 실란의 예로는 일반식 R2Si(OR')2의 실란에 있어서, 디메틸디에톡시실란 또는 디메틸디메톡시실란; 일반식(R2SiO)n(n=3-8임)의 올리고머에 있어서, 옥타메틸시클로테트라실록산 또는 헥사메틸시클로트리실록산, 일반식 RSi(OR')3의 실란에 있어서, 메틸트리메톡시실란, 페닐트리에톡시실란, 3-클로로프로필트리메톡시실란, 3-메르캅토프로필 트리메톡시실란 또는 메타아크릴옥시프로필트리메톡시실란, 일반식 Si(OR')4의 실란에 있어서 테트라메톡시실란 또는 테트라에톡시실란이 있다Examples of suitable silanes include, but are not limited to, silanes of the general formula R 2 Si (OR ') 2 , dimethyldiethoxysilane or dimethyldimethoxysilane; In an oligomer of the general formula (R 2 SiO) n (n = 3-8), methyltrimethoxy in octamethylcyclotetrasiloxane or hexamethylcyclotrisiloxane and silane of the general formula RSi (OR ') 3 . Tetrameth in silane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyl trimethoxysilane or methacryloxypropyltrimethoxysilane, and a silane of the general formula Si (OR ') 4 . There is oxysilane or tetraethoxysilane
그 제조방법의 최종 처리공정에서 이미 설명한 에틸렌불포화모노머는 폴리실록산 그라프트 기재에 그라프팅(grafting)된다.The ethylene-unsaturated monomers already described in the final treatment step of the preparation method are grafted onto the polysiloxane graft substrate.
특허문헌 EP-A 492376에 기재되어 있는 방법에 의해, 물에 용해시킬 수 있거나 또는 모노머에 용해시킬 수 있는 프리래디컬 개시제의 존재하에서 에멀젼 중합에 의해 그라프팅(grafting)이 발생한다.By the method described in patent document EP-A 492376, grafting occurs by emulsion polymerization in the presence of a free radical initiator which can be dissolved in water or in a monomer.
처리공정으로, 오르가노폴리머쉘을 가진 사전에 가교시킨 실리콘 엘라스토머 입자가 수중에서 분산시켜 수용성 분산액의 형태로 얻어진다.In the treatment step, the pre-crosslinked silicone elastomer particles with the organopolymer shell are dispersed in water to obtain a water-soluble dispersion.
그 수용성 분산액의 고형분함량 10-60wt%, 특히 15-50wt%를 갖는 것이 바람직하다.It is preferred to have a solids content of 10-60 wt%, especially 15-50 wt% of the aqueous dispersion.
위 수용성 분산액에서 고형분함량이 너무 많으면 가공성이 불충분하게 되고, 너무 적으면 경제적으로 비효과적이므로 10-60wt%의 범위가 적합하다.Too much solids content in the above aqueous dispersions results in insufficient processability, and too little is economically ineffective, so a range of 10-60 wt% is suitable.
그 실리콘코어의 가교도는 그 탄성을 결정하며, 단위(RSiO3/2) 또는 (SiO4/2)를 얻기 위하여 알콕시실란 및/또는 실록산에 대응하는 출발성분을 적합하게 선택함으로써 통상의 방법으로 특히 얻을 수 있다.The degree of crosslinking of the silicone core determines its elasticity, and in particular by conventional methods by appropriately selecting starting components corresponding to alkoxysilanes and / or siloxanes to obtain units (RSiO 3/2 ) or (SiO 4/2 ). You can get it.
올레핀불포화 2중결합으로 이루어진 실란단위, 예로서 비닐래디컬 또는 3-메타아크릴옥시프로필래디컬의 결합으로 그 오르가노폴리머쉘이 그 다음의 그라프트 중합에서 공유결합에 의해 그 실리콘코어에 화학결합을 하도록 한다.Silane units consisting of olefinically unsaturated double bonds, such as vinyl radicals or 3-methacryloxypropyl radicals, such that the organopolymer shell is chemically bonded to its silicon core by covalent bonds in the subsequent graft polymerization. do.
그 오르가노폴리머쉘(b)의 합성에 적합한 모노머를 선택함으로써 오르가노폴리머쉘의 요구에 따라 적합하게 할 수 있다.By selecting the monomer suitable for the synthesis | combination of the organopolymer shell (b), it can be made according to the request of an organopolymer shell.
예로서, 메틸메타아클리레이트(Tg 높음)와 n-부틸아크릴레이트(Tg 낮음)로 이루어진 코폴리머쉘을 가교시킨 실리콘코어에 그라프팅함으로써, 그 폴리머쉘의 연화온도를 특히 설정할 수 있기 때문에, 그 수용성코팅성분의 처리와 코팅특성에 관련되는 필수 요건에 정확하게 부응시킬 수 있다.For example, by grafting a copolymer core composed of methyl methacrylate (Tg high) and n-butyl acrylate (Tg low) to a crosslinked silicone core, the softening temperature of the polymer shell can be set particularly. It can accurately meet the essential requirements related to the treatment and coating properties of the water-soluble coating component.
예로서, 메틸메타아크릴레이트와 글라시딜 메타아크릴레이트로 이루어진 코폴리머쉘을 가교시킨 실리콘코어에 그라프팅(grafting)시킴으로써 한편으로는 글리시딜메타아크릴레이트로 도입시키는 에폭시드 작용에 의해 수용성 코팅 조성물의 바인더수지와 개질제 입자사이에서 매트릭스 결합을 얻을 수 있고, 또 다른 한편으로는 이들의 개질제입자가 폴리에스테르수지를 기재로 한 바인더에서 가교제로 작용할 수 있다.For example, a water-soluble coating by grafting a copolymer shell consisting of methyl methacrylate and glycidyl methacrylate onto a crosslinked silicone core and introducing glyceride methacrylate on the one hand into the glycidyl methacrylate. Matrix bonds can be obtained between the binder resin and the modifier particles of the composition, and on the other hand, these modifier particles can act as crosslinking agents in binders based on polyester resins.
따라서,(R2SiO2/2)x· (RSiO3/2)y(여기서 x=80-99㏖%, y=1-20㏖%, R은 같거나 다르며, 메틸 및/또는 3-메타아크릴옥시프로필 임)로 이루어진 코어와, 폴리(메틸메타아크릴레이트)쉘 또는 메틸메타아크릴레이트와 부틸아크릴레이트 및/또는 글리시딜메타아크릴레이트로 이루어진 코플리머쉘을 가진 가교시킨 실리콘엘라스토머 코폴리머 입자가 가장 바람직하다.Thus, (R 2 SiO 2/2 ) x · (RSiO 3/2 ) y (where x = 80-99 mol%, y = 1-20 mol%, R is the same or different, methyl and / or 3-meta Crosslinked silicone elastomer copolymer particles having a core composed of acryloxypropyl) and a copolymer shell composed of poly (methyl methacrylate) shell or methyl methacrylate and butyl acrylate and / or glycidyl methacrylate. Most preferred.
그 코폴리머 중량 전체를 기준으로 하여 코어폴리머의 중량비는 50-80wt%가 특히 바람직하며, 그 오르가노폴리머쉘의 중량비는 20-50wt%가 특히 바람직하다.Particularly preferably, the weight ratio of the core polymer is 50-80 wt%, and the weight ratio of the organopolymer shell is 20-50 wt% based on the total weight of the copolymer.
이것은 오르가노폴리머의 그라프팅도 25-100%에 대응한다.This corresponds to 25-100% grafting of organopolymers.
오르가노폴리머쉘을 가진 사전에 가교시킨 실리콘 엘라스토머 코폴리머입자의 부가특성과 수용성 분산액으로서의 혼합용이성으로 인하여, 수용성 코팅재의 모든 통상의 바인더계에 사용할 수 있다.Due to the additional properties of pre-crosslinked silicone elastomer copolymer particles with organopolymer shells and ease of mixing as an aqueous dispersion, they can be used in all conventional binder systems of water-soluble coating materials.
수용성 코팅재의 바인더계의 예로는 물에 용해시킬 수 있는 바인더에 있어서, 개질알키드수지, 아크릴레이트수지, 선상 또는 분기상포화 폴리에스테르수지, 에폭시수지, 쉘락(shellac) 및 변성페놀수지가 있다.Examples of the binder system of the water-soluble coating material include modified alkyd resins, acrylate resins, linear or branched saturated polyester resins, epoxy resins, shellac and modified phenol resins.
물에 희석시킬 수 있는 바인더의 예로는(선택적으로 개질시킴) 분산 또는 물에 희석시킬 수 있는 불포화 및 포화 폴리에스테르수지, 알키드수지에멀젼, 폴리우레탄분산액, 1성분 에폭시수지에멀젼, 유화시킬 수 있는 2성분 에폭시수지계, 분산시킬 수 있는 알키드, 페놀, 멜라민 및 우레아수지, (메타)아크릴레이트분산액, (메타)아크릴레이트코폴리머분산액, 폴리스티렌 및 스티렌코폴리머분산액, 폴리(비닐에스테르)분산액, 폴리비닐클로리드 및 폴리비닐리덴 클로리드분산액이 있다.Examples of binders that can be diluted in water (optionally modified) include unsaturated and saturated polyester resins, alkyd resin emulsions, polyurethane dispersions, one-component epoxy resin emulsions, two emulsifiers that can be dispersed or diluted in water. Component epoxy resin, dispersible alkyd, phenol, melamine and urea resin, (meth) acrylate dispersion, (meth) acrylate copolymer dispersion, polystyrene and styrene copolymer dispersion, poly (vinyl ester) dispersion, polyvinyl chloro Lead and polyvinylidene chloride dispersions.
개질(modification)에 있어서, 오르가노폴리머쉘을 가진 사전에 가교시킨 실리콘 엘라스토머 코콜리머입자를 수용성 분산액의 형태로, 바람직하게는 실리콘 엘라스토머 성분과 바인더성분의 전체 중량을 기준으로 하여 각각의 경우 실리콘 엘라스토머프랙션(코폴리머입자)0.5∼50wt%, 바람직하게는 1.0∼3.0wt%의 분산액 분말로서 그 수용성 코팅조성물에 첨가하는 것이 바람직하다.In the modification, the pre-crosslinked silicone elastomer cocopolymer particles with the organopolymer shell are in the form of an aqueous dispersion, preferably in each case silicone based on the total weight of the silicone elastomer component and the binder component. Elastomer fraction (copolymer particles) is preferably added to the water-soluble coating composition as a dispersion powder of 0.5 to 50 wt%, preferably 1.0 to 3.0 wt%.
즉, 그 사전에 가교시킨 실리콘 엘라스토머 코폴리머입자의 양이 너무 적을 경우 효과를 얻을 수 없고, 너무 많을 경우 비경제적이며 코팅의 품질을 감소시키므로 그 코폴리머의 입자의 사용량은 0.5-50wt%의 범위가 적합하다.In other words, if the amount of the crosslinked silicone elastomer copolymer particles is too small, no effect can be obtained, and if the amount is too large, it is uneconomical and reduces the quality of the coating, so the amount of the particles of the copolymer is 0.5-50 wt%. Is suitable.
수용성 코팅재에 적합한 조성물은 통상의 기술자에게 공지되어 있다(예로서, H. Kittel(ed.), Lehrbuch der Lacke und Beschichtungen, volume Ⅳ, Verlag W.A. Colomb, Berlin, Oberschwandorf, 1976).Compositions suitable for water-soluble coatings are known to the skilled person (eg, H. Kittel (ed.), Lehrbuch der Lacke und Beschichtungen, volume IV, Verlag W. A. Colomb, Berlin, Oberschwandorf, 1976).
그 첨가처리는 교반기 또는 분산장치를 사용하여 수용성 코팅재를 조성시키는 통상의 처리공정에 따라 실시한다.The addition treatment is carried out in accordance with a conventional treatment step of forming a water-soluble coating using a stirrer or a dispersion device.
오르가노폴리머쉘을 가진 사전에 가교시킨 실리콘 엘라스토머의 수용성 분산액은 이 경우, 바인더, 물, 가교제, 촉매, 안료, 점도부여제, 필러 등 수용성 코팅조성물의 성분으로 필요로 하는 순서에 따라 혼합시킬 수 있다.Aqueous dispersions of pre-crosslinked silicone elastomers with organopolymer shells may in this case be mixed in the required order as components of the water-soluble coating composition, such as binders, water, crosslinkers, catalysts, pigments, viscosifiers and fillers. have.
혼합(배합)온도 +1℃ ∼ +90℃, 특히 +5℃ ∼ +60℃의 범위에서 실시하는 것이 바람직하다.It is preferable to carry out in mixing (mixing) temperature +1 degreeC-+90 degreeC, especially the range of +5 degreeC-+60 degreeC.
이 발명에 의한 개질시킨 수용성 코팅재는 통상의 용매를 기재로 한 코팅재 또는 개질시키지 않은 수용성 코팅재를 사용하는 어떤 경우에 있어서도 원칙적으로 사용할 수 있다.The modified water-soluble coating material according to the present invention can be used in principle in any case of using a conventional solvent-based coating material or an unmodified water-soluble coating material.
이들의 코팅재는 대형 철제구조물(즉, 교량, 탱크, 크레인 및 이송장비, 파이프배관, 광물 및 오일추출장비, 철제부품, 화학플랜트의 부품)의 금속코팅, 자동차분야(클리어코트, 톱코트, 내장다듬질, 다듬질면, 석제칩보호 및 하부기체보호, 자동차, 로리, 버스, 건축현장 및 농업용차량의 재다듬질)의 금속 및 철도차량, 화물콘테이너, 항공기, 선박(각각의 외부 다듬질)의 금속의 코팅 및 또 다른 처리(코일코팅)전금속기재, 가정용 가전제품(즉, 냉동기, 냉장고, 디쉬세척기, 세탁기, 전기오븐용) 및 금속제포장(즉 드럼, 용기 등)의 코팅용에 특히 적용한다.These coatings include metal coatings for large steel structures (ie bridges, tanks, cranes and transport equipment, pipe piping, mineral and oil extraction equipment, steel parts, and chemical plant parts), automotive applications (clear coats, top coats, interiors). Coating of metals in finishing, finishing surfaces, stone chip protection and underbody protection, refinishing of automobiles, lorry, buses, construction sites and agricultural vehicles), railway vehicles, cargo containers, aircraft, ships (each external finishing) And other treatments (coil coating), in particular for the coating of all metal substrates, household appliances (ie for refrigerators, refrigerators, dishwashers, washing machines, electric ovens) and for metal packaging (ie drums, containers, etc.).
이들의 코팅재는 또 가구(목재가구, 금속재가구, 램프하우징 등), 내외장용 건재성분(목재, 강재, 비철금속 및 비철합금, 플라스틱, 콘크리트, 모르타르 및 플라스터, 즉 창프레임, 외측패널, 도어, 게이트(gates), 홈통장치, 플로어, 계단, 건물의 표면구성성분, 벽, 천장, 히터 및 래디에이터, 탱크, 배선), 자전거(cycles), 간판(sings), 휠림(wheel rims)까지 코팅에 사용된다.These coatings also include furniture (wood furniture, metal furniture, lamp housings, etc.), interior and exterior building materials (wood, steel, non-ferrous and non-ferrous alloys, plastics, concrete, mortars and plaster, ie window frames, outer panels, doors, gates). for coatings (gates), gutters, floors, stairs, building surface components, walls, ceilings, heaters and radiators, tanks, wiring, cycles, signs, wheel rims do.
위 예시의 테스트 결과, 그 수용성 코팅재의 인성(toughness)(충격)이 오르가노폴리머쉘을 가진 사전에 가교시킨 실리콘 엘라스토머 코폴리머 입자를 첨가시킴으로써 향상되었고, 코팅계의 접착 및 이들의 표면특성의 효과가 없었고, 코팅계의 경도에 약간의 효과만을 나타내었다.As a result of the above test, the toughness (impact) of the water-soluble coating was improved by adding pre-crosslinked silicone elastomer copolymer particles having an organopolymer shell, and the effect of adhesion of the coating system and their surface properties. There was no and only a slight effect on the hardness of the coating system.
대비실시예에서, 오르가노폴리머쉘이 없는 실리콘 엘라스토머 입자의 첨가가 인성(충격)을 향상시켜도 코팅재의 경도와 이들의 표면 특성에서 현저한 역효과를 가짐을 나타내었다.In a comparative example, the addition of silicone elastomer particles without organopolymer shells has shown to have a significant adverse effect on the hardness of the coatings and their surface properties even when the toughness (impact) is improved.
그 결과, 조정한 미상분리(microphase separation)만이 아니라 건조시킨 코팅필름에서 그 폴리머 매트릭스와 개질제입자의 우수한 사용성을 필요로 한다.As a result, not only the adjusted microphase separation but also the good usability of the polymer matrix and the modifier particles in the dried coating film is required.
실시예에서 결과가 우수한 이유는 가교시킨 실리콘상(silicone phase)으로 인하여 이 발명의 그 충격개질제(impact modifier)가 일정한 입자크기와 형태를 가진 각각의 미상(microphase)형태의 열가소성 또는 열경화성계에 결합되기 때문이다.The good results in the examples are due to the crosslinked silicone phase that the impact modifier of this invention binds to each microphase type of thermoplastic or thermoset system with a constant particle size and shape. Because it becomes.
상분리(phase separation)를 완전하게 할 경우에만 그 폴리머 매트릭스의 바람직하지 않은 연화가 없으며, 그 결과 경도, 치수안정도 및 기계적 강도 등 폴리머 매트릭스의 특성에 대한 역효과가 상실된다.Only complete phase separation results in undesired softening of the polymer matrix, resulting in the loss of adverse effects on the properties of the polymer matrix such as hardness, dimensional stability, and mechanical strength.
또, 그 오르가노폴리머쉘이 코팅바인더의 폴리머 매트릭스와 입자상 개질제의 우수한 상용성을 갖도록 한다.In addition, the organopolymer shell has excellent compatibility with the polymer matrix of the coating binder and the particulate modifier.
그 오르가노폴리머쉘은 분산액 형태의 사전에 가교시킨 실리콘 엘라스토머입자와 물에 용해시킬 수 있거나 물에 희석시킬 수 있는 바인더의 혼화성/콜로이드상의 상용성에 절대적으로 필요한 것은 아니다.The organopolymer shell is not absolutely necessary for the compatibility of the miscible / colloidal phases of pre-crosslinked silicone elastomer particles in dispersion form with binders that can be dissolved or diluted in water.
그러나, 그 오르가노폴리머쉘은 건조후 그 매트릭스와 그 입자의 폴리머 상용성에 필요하다.However, the organopolymer shell is required for polymer compatibility of the matrix with the particles after drying.
그 입자구조와 그 입자의 폴리머 상용성은 그 입자직경에 의한 그 개질재 상의 주요한 크기의 정밀한 구성을 제공한다.The particle structure and the polymer compatibility of the particles provide a precise configuration of the major size on the modifier by the particle diameter.
그 사전에 가교시킨 실리콘 엘라스토머 코폴리머 입자가 오르가노폴리머 쉘과 완전하게 그라프팅 됨으로 오염문제, 접착문제, 침전문제 및 유동결점이 발생하지 않는다.The pre-crosslinked silicone elastomer copolymer particles are grafted completely with the organopolymer shell, thus eliminating contamination, adhesion problems, sedimentation problems and flow defects.
그 결과 얻어진 코팅은 오버코팅을 할 수 있다.The resulting coating can be overcoated.
이 발명을 구체적으로 설명하기 위하여 다음 실시예를 예시한다.The following examples are illustrated to specifically illustrate this invention.
실시예 1-2, 대비실시예 1-3:Example 1-2, Comparative Example 1-3:
실시예 1-2 및 대비실시예 1-3에서는 다음표 1에 기재된 조성을 가진 폴리에스테르 코팅 조성물을 제조하였다.In Example 1-2 and Comparative Example 1-3 was prepared a polyester coating composition having the composition shown in Table 1.
이 발명에 의한 실시예에서 분산액 A를 사용하였고, 대비실시예 2 및 3에서 분산액 B를 사용하였다.Dispersion A was used in the examples according to this invention, and dispersion B was used in comparative examples 2 and 3.
대비실시예 1의 코팅조성물은 통상의 개질하지 않은 수용성 코팅재의 조성물에 대응한다.The coating composition of Comparative Example 1 corresponds to a composition of a conventional unmodified water soluble coating material.
분산액 A.Dispersion A.
[R2SiO2/2]x· [R'SiO3/2]y(x= 95mo1%, y=5㏖%, R은 메틸, R'은 메틸 및 3-메타아크릴옥시프로필임)로 이루어진 코어와 폴리메틸메타아크릴레이트쉘(PMMA 그라프팅도 50wt%)를 가진 실리콘입자의 수용성 분산액:[R 2 SiO 2/2 ] x [R'SiO 3/2 ] y (x = 95mo1%, y = 5mol%, R is methyl, R 'is methyl and 3-methacryloxypropyl) Aqueous dispersion of silicone particles with core and polymethylmethacrylate shell (50 wt% PMMA grafting degree):
그 주요한 입자크기는 약 100㎚이고, 오르가노폴리머쉘을 가진 실리콘입자의 고형분함량은 26.3%이다.Its main particle size is about 100 nm and the solids content of silicon particles with organopolymer shell is 26.3%.
분산액 B :Dispersion B:
[R2SiO2/2]x· [R'SiO3/2]y(x= 95mo1%, y=5㏖%, R은 메틸임)로 이루어진 실리콘입자의 수용성 분산액; 주요한 입자크기는 약 100㎚이고, 그 실리콘입자의 고형분함량은 19%이다.An aqueous dispersion of silicon particles composed of [R 2 SiO 2/2 ] x [R'SiO 3/2 ] y (x = 95mo1%, y = 5mol%, R is methyl); The major particle size is about 100 nm and the solid content of the silicon particles is 19%.
다음의 표 1에 나타낸 수용성 코팅 조성물(실시예 1-2, 대비실시예 1-3)을 제조하기 위하여, 그 조성물에서의 특정의 성분과 함께 실온에서 20-30분간 용해 기(dissolver)에 의해 혼합하였다.To prepare a water-soluble coating composition (Examples 1-2, Comparative Examples 1-3) shown in Table 1 below, with a specific component in the composition, a dissolver at room temperature for 20-30 minutes. Mixed.
테스트하기 위하여, 그 수용성 코팅 조성물은 나선형 필름 인발용 닥터블레이드(spiral film drawing doctor blade)에 의해 금속패널에 처리하였다.For testing, the water soluble coating composition was treated to a metal panel by a spiral film drawing doctor blade.
실온(22℃)에서 건조시킨 다음, 테스트를 패널 처리 3일후에 실시하였다.After drying at room temperature (22 ° C.), the test was performed 3 days after the panel treatment.
그 테스트 결과를 다음표 1에 나타낸다.The test results are shown in Table 1 below.
다음의 테스트 방법을 사용하였다.The following test method was used.
표면특성:Surface characteristics:
그 표면특성은 그 필름 표면의 육안평가에 의해 정량평가를 하였다.The surface characteristics were quantitatively evaluated by visual evaluation of the surface of the film.
오버 코팅 적합성 (덧칠 적합성 ) (overcoatability):Overcoatability:
오버코팅 적합성을 평가하기 위하여, 실시예 1, 2 및 대비실시예 1-3의 코팅조성물로 코팅시킨 금속패널을 각각의 경우 동일한 코팅 조성물로 다시 오버코팅을 하였다.In order to evaluate the overcoating suitability, the metal panels coated with the coating compositions of Examples 1 and 2 and Comparative Examples 1-3 were in each case overcoated again with the same coating composition.
그 오버코팅 적합성은 육안관찰에 의해 정량평가를 하였다.The overcoating suitability was quantitatively evaluated by visual observation.
인터코트 접착(intercoat adhesion)을 측정하기 위하여 3일간 건조후 펜 나이프(pen knife)를 사용하여 필링(peeling)시켜 상부 코팅필름을 부분제거할수 있는 지의 여부조사를 하였다.In order to measure intercoat adhesion, it was examined whether or not the top coating film could be partially removed by peeling with a pen knife after drying for 3 days.
그 인터코트 접착은 관찰할 때마다 이탈이 없을 때 "좋음" 으로 평가하였다.The intercoat adhesion was evaluated as "good" when there was no deviation with every observation.
역충격 (reverse impact):Reverse impact:
역충격은 에리히센(Erichsen) 볼충격(ball impact) 시험장치의 타입 304를 사용하여 볼충격 테스트에 의해 측정하였다.Reverse impact was measured by ball impact test using a Type 304 of Erichsen ball impact test apparatus.
쾨니그 진자경도(Knig pendulum hardress):König Pendulum Hardness (K nig pendulum hardress):
쾨니그 진자경도는 DIN53137에 의해 테스트하였다.König pendulum hardness was tested to DIN53137.
에리히센 압흔(Erichsen indentation):Erichsen indentation:
에리히센 압흔은 DIN ISO 1520에 의해 테스트하였다.Erichsen indentation was tested according to DIN ISO 1520.
크로스-해치 (Cross-hatch):Cross-hatch:
크로스 해치는 DIN 53151의 방법에 의해 측정하였다.The cross hatch was measured by the method of DIN 53151.
그 결과, PMMA 쉘(실시예 1 및 2)을 가진 이 발명에 의한 실리콘 엘라스토머 입자를 첨가함으로써 (충결)인성(역충격)이 현저하게 향상되고, 필름경도에서 약간의 감소만을 가지며 그 필름의 표면특성과 접착에 있어서 역효과가 없음을 나타내었다.As a result, the addition of the silicone elastomer particles according to the present invention with PMMA shells (Examples 1 and 2) significantly improved (filling) toughness (reverse impact), with only a slight decrease in film hardness and the surface of the film. There was no adverse effect on the properties and adhesion.
오르가노폴리머쉘이 없는 실리콘 엘라스토머 입자(대비실시예 2,3)을 사용할 경우(충격)인성이 대비할 수 있는 정도로 향상되나, 필름경도, 표면특성 및 오버코팅후 접착은 역효과가 현저하였다.In the case of using the silicone elastomer particles without the organopolymer shell (Comparative Examples 2 and 3) (impact), the toughness is improved to the level that can be prepared, but the film hardness, the surface properties, and the adhesion after the overcoating have a significant adverse effect.
[표 1]TABLE 1
비고: a)지방산 개질폴리에스테르 수지(Httenes-AlbertusNote: a) fatty acid modified polyester resin (H ttenes-albertus
Lackrohstoffe)Lackrohstoffe)
b)TiO2안료(Kronos-Titan)b) TiO 2 pigment (Kronos-Titan)
c)폴리아크릴레이트기재 점도부여제(Kronos-Titan)c) polyacrylate-based viscosity imparting agent (Kronos-Titan)
[실시예 3 및, 대비실시예 4]Example 3 and Comparative Example 4
2성분 에톡시수지코팅재를 기재로 한 수용성 코팅재를 테스트하는 것을 제외하고는 실시예 1, 2 및 대비실시예 1-3에서와 같은 처리공정으로 각각 실시하였다.Except for testing the water-soluble coating material based on the two-component ethoxy resin coating material was carried out in the same treatment process as in Examples 1, 2 and Comparative Examples 1-3.
이 발명에 의한 실시예 3 및 4에서 분산액 A를 개질용으로 다시 사용하였다.In Examples 3 and 4 according to this invention dispersion A was again used for reforming.
대비실시예 4 의 코팅조성물은 개질되지 않았다.The coating composition of Comparative Example 4 was not modified.
다음표 2에 나타낸 수용성 코팅 조성물을 제조하기 위하여(실시예 3-4, 대비실시예 4) 그 조성물에 특정된 성분을 대기온도에서 20-30분간 용해기에 의해 동시에 같이 혼합하였다.To prepare the water-soluble coating composition shown in Table 2 (Example 3-4, Comparative Example 4), the components specified in the composition were mixed together by dissolving for 20-30 minutes at ambient temperature.
그 수용성 코팅 조성물을 알루미늄 패널과 금속패널에 나선형 필름인발 닥터 블레이드에 의해 처리하였다.The water-soluble coating composition was treated to aluminum panels and metal panels by a spiral film drawing doctor blade.
대기온도(22℃)에서 건조를 하였다.It dried at atmospheric temperature (22 degreeC).
패널처리후 3일후에 위에서 설명한 테스트 설명서와 동일한 방법으로 하여 테스트를 하였다.Three days after the panel treatment, the test was conducted in the same manner as the test manual described above.
그 테스트 결과를 다음의 표 2에 나타낸다.The test results are shown in Table 2 below.
그 결과에서 PMMA 셀을 가진 이 발명에 의한 실리콘 엘라스토머 입자(실시예 3,4)를 첨가함으로써 (충격)인성(역충격)이 현저하게 향상되었고 필름경도에 있어서 약간의 감소만을 가짐을 나타내었다.The results showed that the addition of the silicone elastomer particles (Examples 3 and 4) according to the invention with PMMA cells significantly improved the (impact) toughness (reverse impact) and had only a slight decrease in film hardness.
[표 2]TABLE 2
비고:Remarks:
a) 비스페놀 A/F를 기재로 한 2성분 에폭수지 코팅재(Air products)a) Bicomponent epoxy resin coatings based on bisphenol A / F (Air products)
b) 지방산에스테르를 기재로 한 레벨링재(levelling agents)(Borchers)b) leveling agents (Borchers) based on fatty acid esters
c) TiO2안료c) TiO 2 pigment
d) 바륨설페이트 기재필러(Sachtleben)d) barium sulfate base filler (Sachtleben)
e) 폴리아민 부가생성물 경화제(Air products)e) polyamine adduct hardeners (Air products)
이 발명에 의해 개질시킨 코팅재는 대형철제 구조물(교량, 탱크, 크레인 및 이송장비 등)의 금속코팅, 자동차분야의 금속 및 철도차량, 화물콘테이너, 항공기, 선박 등의 금속의 코팅, 금속기재, 가정용 가전제품 및 금속제 포장의 코팅용에 사용할 수 있다.The coating material modified by the present invention is a metal coating of large steel structures (bridges, tanks, cranes and transport equipment, etc.), metal and railway vehicles in the automotive field, coating of metals such as cargo containers, aircraft, ships, metal base, household It can be used for coating of household appliances and metal packaging.
또, 이 발명의 개질시킨 코팅재는 가구, 내외장용 건재성분, 자전거(cycles), 간판(signs 및 휠림(wheel rims)의 코팅에 사용할 수 있다.In addition, the modified coating of the present invention can be used for the coating of furniture, interior and exterior building material components, bicycles, signs and wheel rims.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19617379A DE19617379A1 (en) | 1996-04-30 | 1996-04-30 | Pre-crosslinked silicone elastomer particles with an organopolymer shell as a formulation component in aqueous paint preparations |
| DE19617379.5 | 1996-04-30 | ||
| PCT/EP1997/002093 WO1997041183A1 (en) | 1996-04-30 | 1997-04-24 | Previously cross-linked silicone elastomer particles with an organopolymer sheath as a constituent for formulating aqueous lacquer compositions |
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| KR20000065082A KR20000065082A (en) | 2000-11-06 |
| KR100301382B1 true KR100301382B1 (en) | 2001-11-22 |
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| KR1019980708663A KR100301382B1 (en) | 1996-04-30 | 1997-04-24 | A water-soluble coating composition based on a binder which can be dissolved or diluted in water made of silicone elastomer copolymer particles crosslinked in advance with an organopolymer shell, and a method of manufacturing the same. |
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| US (1) | US6147142A (en) |
| EP (1) | EP0882105B1 (en) |
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| KR (1) | KR100301382B1 (en) |
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| AU (1) | AU710726B2 (en) |
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| DE (2) | DE19617379A1 (en) |
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- 1997-04-24 AU AU27697/97A patent/AU710726B2/en not_active Ceased
- 1997-04-24 US US09/155,370 patent/US6147142A/en not_active Expired - Fee Related
- 1997-04-24 CN CN97194200A patent/CN1217009A/en active Pending
- 1997-04-24 KR KR1019980708663A patent/KR100301382B1/en not_active IP Right Cessation
- 1997-04-24 CA CA002251692A patent/CA2251692A1/en not_active Abandoned
- 1997-04-24 DE DE59700758T patent/DE59700758D1/en not_active Expired - Fee Related
- 1997-04-24 JP JP9538560A patent/JPH11508641A/en active Pending
- 1997-04-24 WO PCT/EP1997/002093 patent/WO1997041183A1/en active IP Right Grant
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Also Published As
| Publication number | Publication date |
|---|---|
| DE59700758D1 (en) | 1999-12-30 |
| ES2142162T3 (en) | 2000-04-01 |
| EP0882105A1 (en) | 1998-12-09 |
| EP0882105B1 (en) | 1999-11-24 |
| DE19617379A1 (en) | 1997-11-06 |
| AU710726B2 (en) | 1999-09-30 |
| JPH11508641A (en) | 1999-07-27 |
| CN1217009A (en) | 1999-05-19 |
| KR20000065082A (en) | 2000-11-06 |
| AU2769797A (en) | 1997-11-19 |
| WO1997041183A1 (en) | 1997-11-06 |
| CA2251692A1 (en) | 1997-11-06 |
| US6147142A (en) | 2000-11-14 |
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